Synthetic lubricants



Patented Mar. 14, 1950 SYNTHETIC LUBRICANTS William E. Garwood, Haddonfleld, Francis M. Seger, Pitman, and Alexander N. Sachanen, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorp New York orated, a corporation of No Drawing. Application December 11, 1948, Serial No. 64,904

Claims. (Cl. 260-139) This invention has to do with the condensation of normal, alpha mono-olefins, certain conjugated hydrocarbons and phosphorus sulfides, and particularly has to do with the new and useful compositions obtained by said condensation.

As is well known to those familiar with the art, olefins have previously been polymerized. So also have conjugated hydrocarbons. Each of these unsaturated materials has previously been reacted individually with sulfur and with phosphorus sulfides. Olefin polymers and olefin-conjugated diolefin collolymers have also been reacted with phosphorus sulfides. Oleflns and conjugated hydrocarbons have previously been reacted together. In the latter instance, copolymerization is generally incomplete. For example, when decene-l and styrene are copolymerized at 600 R, an 011 containing a polystyrene cloud at room temperature (-25 C.) is formed- As described in our copending application Serial No. 33,438, filed June 16, 1948, of which this application is a continuation-in-part, it has been found that normal alpha mono-olefins condense with certain conjugated hydrocarbons and sul fur to form highly desirable viscous oils. The oils so formed are free from the shortcomings of olefin-conjugated hydrocarbon copolymers, as

illustrated by the styrene-decene-1 copolymer thetic lubricating oils, for use alone or blended referred to above. It has now been discovered I that similarly characterized viscous oils are obtained by condensing normal, alpha mono-olefins, and conjugated hydrocarbons with phosphorus sulfides and/or with elemental phosphorus and sulfur, under the conditions of operation described below. The viscous oils of this invention are unusually stable. Catalytic oxidation stability tests demonstrate them tobe superior to condensationproducts of decene-l alone, and superior to condensation products of decenc- 1 and styrene. The characteristics of the new with other lubricants.

REACTANTS As indicated above, the mono-olefin reactants of this invention are normal or straight chain alpha mono-olefins and contain from six to fourteen carbon atoms. Such mono-olefins are normally-liquid at temperatures of the order of 20-25 C. Illustrative of such. mono-olefins are the following: hexene-l, octene-l, decene-l, dodecene-l, tetradecene-l, and the like. Preferred, however, of such olefins are those having from eight to twelve carbon atoms, with decene-l'representing a particularly desirable olefin. It will be clear from the foregoing examples that an alpha olefin may also be referred to as a l-olefin.

Not only may the mono-olefins of the aforesaid character be used individually in this invention, but they may also be used in admixture with each other. In addition, olefin mixtures containing a substantial proportion of such mono-olefins may be used. Preferred of such mixtures are those contaning a major proportion of a l-olefin or of l-olefins. Representative of such mixtures are those obtained by the cracking of parafiln waxes and other paraflin products, and those obtained from the Fischer-Tropsch and related processes.

These hydrocarbon mixtures may contain, in addition to the l-olefin or l-olefins, such materials as: other olefins, parafiins, naphthenes and aromatics.

The conjugated reactants contemplated herein are conjugated hydrocarbons and derivatives thereof, wherein the conjugated system is represented by the grouping:

Of such conjugated hydrocarbons, styrene has been found to be particularly desirable for the purposes of this invention. These conjugated hydrocarbons are characterized by at least one vinyl group, 4

in a 1:3 conjugated relationship with another the foregoing conjugated materials are hydrocarbons.

Derivatives of the conjugated hydrocarbons. or substituted conjugated hydrocarbons, which typify those contemplated herein are: halogensubstituted materials such as chloroprene (2- chloro-butadiene), l-bromo butadiene and pchloro styrene; alkoxy substituted materials such as p-methoxy styrene; etc. As will be noted from the character of the foregoing typical substituted conjugated hydrocarbons, substituent groups which may be present are those which do not interfere with the course of the condensation of the conjugated system with the aforesaid 1- olefin and phosphorus sulfide. In other words, a substituent group which may be present on the conjugated hydrocarbon is one which is substantially inert or unreactive in the condensation. The substituent group, however, generally modilies the character of the oil product; yet,in all cases, the products are characterized by unusual stability and are useful as lubricants. For example, when chloroprene or p-chloro styrene is used, the synthetic lubricant formed is also char-.

acterized by extreme pressure properties.

In connection with divinyl benzene, which may be used as a conjugated reactant, it should be noted that this reactant is characterized by a high degree of reactivity in view of the two vinyl groups. For most satisfactory results with divinyl benzene, a relatively small quantity should be used with a l-mono-olefin and a phosphorus sulfide. Accordingly, in the discussion of reaction proportions hereinafter, it should be recognized that the quantity of divinyl benzene used will generally be at the lower end of the conjugated reactant proportion range.

It will be understood, of course, that mixtures of the aforesaid conjugated hydrocarbons, and their aforesaid derivatives, may be used in place of the individual reactant. Similarly, mixtures containing substantial, and preferably major, proportions of one or more of said conjugated reaotants may be used. Examples of such mixtures are: a crude styrene containing ethyl benattend? in a 1:3 conjugatedrelationshlp with another double bond.

Preferred of the coniusated reactants are vi yl aromatic hydrocarbons, with particular preference being given-to styrene.-

g .The phosphorus and sulfur reactant may be in the form of elemental phosphorus and elemental sulfur or in the form of a phosphorus sulfide. All of the phosphorus sulfides are contemplated herewith, included among which are: P388 (or PS2) Pisa (01' Pass) P482, P255, PiSz, P4810, etc.

Particularly advantageous in providing outstanding synth tic oils is PzSs, which represents the preferred reactant. When elemental phosphorus and elemental sulfur are used under the conditions of operation described below, it is quite possiblethat phosphorus sulfide or phosphorus sulfldes are formed in situ. It willbe understood that elemental phosphorus and/ or elemental sulfur may be used with one or more of the phosphorus sulfides in the preparation of a synthetic oil.

REACTION commons being used for the longer reaction periods. How= ever, the reaction period will also be influenced by the nature of the reactants and the quantity of reactant used.

Pressures ranging from atmospheric to 4000 pounds per square inch may be used. In general, it is desirable to use sufiicient pressure to maintain the reactants in liquid state.

For synthetic lubricants of very high viscosity index, higher temperatures than about 750 F. are to be avoided, inasmuch as it has been observed that the V. I. decreases with increase of temperature.

The proportion of reactants used is a critical factor in preparing the synthetic lubricants contemplated herein. With one molar proportion of a normal, alpha mono-olefin as the basis, from about 0.01 to about 1.0 molar proportion of conjugated reactant and from about 0.01 to about '10 per cent, by weight of total olefins, of phosphorus sulfide provide satisfactory products. Preferred proportions. however, are from about 0.05 to about 0.5 molar proportion of conjugated reactant and from about 0.05 to about 1 per cent, by Weight of total olefins, of phosphorus sulfide, with one molar proportion of normal, alpha monoolefin. The preference for the latter range of proportions is influenced by the outstanding character of the lubricants obtained by selecting proportionswithin this range. Generally, synthetic lubricants obtained while operating within the preferred range are characterized by higher viscosity indices, lower acidity as measured by neutralization numbers (N. N.) and lower phosphorus and sulfur contents. When elemental phosphorus and elemental sulfur are used. in place of a phosphorus sulfide, the combined quantity of phosphorus and sulfur will correspond to the quantities recited above for a phosphorus sulfide, namely 0.01- per cent and preferably 0.05-1 per cent, by weight of total oleflns (conjugated reactant and mono-olefin) The ratio of phosphorus to sulfur used 'is preferably 2 parts phosphorus to.5 parts sulfur.

In all cases, however, whenever elemental phosphorus and elemental sulfur are used in the absence of a phosphorus sulfide or either or both are used with such sulfide, the combined quantity should not exceed the maximum recited above for a phosphorus sulfide, namely, 10 per cent by weight of total olefins.

It will be understood. of course, that the condensation is aided by providing mixing of the reactants. This may be provided by using various agitating means which are well known in the art.

EXAMPLES In order to illustrate the principles oi this invention, the results of a series of typical, and

. non-limiting, condensations are set forth in tabular form in Table I below. These condensations were carried out in a rocking-type bomb (American Instrument 00.). The reactants were charged to the bomb, which was then heated to the desired temperature for the desired length of time. Thereafter, the bomb was cooled, and

discharged. The contents of the bomb were veeuum topped to remove u'nreacted hydrocarbons and materials of low molecular weight. It should be noted that the reaction times, recited as "Time, hours in Table I, represent the time intervals during which the bomb was maintained at the desired temperature, and do not include the time intervals necessary to heat the bomb and its contents to the desiredtemperature, and do not include the time intervals necessary to cool the I bomb after heat to the bomb has been discontinued.

The condensation products discharged from the bomb, or other reaction vessel, were topped and filtered, as in the runs shown in Table I. To distinguish the condensation products from the distillate fractions thereof, the refinedoils are identified as residual oils. The latter term identifies the oils from which unreacted materials and products of intermediate boiling range have been separated.

All of the tests and analyses to which the residual oils in Table I were subjected are well known standard tests. In this connection, it will be noted that the designation "N. N." refers to the neutralization number, which is a measure of the acidity of the oil.

Styrene used in these condensations contained a fraction of one per cent of p-tertiary-butyl catechol, the latter acting as a stabilizer or polymerization inhibitor. This styrene material is the commercial product now available.

Table I Run No l Olefin Decene-l Parts by Weight 280 Decenc ln Deoene-L. 264 280 Molar Proportion. Conjugated System yrene. 25

Phosphorus n Parts by Weight Molar Pro ortion Wt. Per ent of Total Oleflns r Sulf Parts by Weight Molar Pro oniofiIIIIIII Wt. Per ent of Total Oleflm Temperature, F Time, Hrs. Max. Pressure, p. s. i. g..

Topping of Reaction Product:

Max. Vapor Temp., O-

Pressure, mms. Hg

Residual Oil:

Parts by Wei ht Pour Point F re a peci 0 rev y Color (Lovibond) Per Cent P Per Cent 8 Cloud Point, F.

Table I-Continued Run No Olefin Deeene-L. Deeene-L. Decene-L. Decene-LpOctene-l... Omens-2.. Z-Ethyl Decene-1 Dccene-i Parts by Weight 280 280 Molar Proportion Co ugated System arts by Weight" 2.0 2 Butadiene Phosxphorus arts by Weight: Molar Pro ortion Parts by Weight Molar Pro ortlon Wt. Per ent oi Total Ole fins Temperature, F. Time, Hrs Mex. Pressure, p.

Top ing 0! Reaction Pro uct:

Max. Vapor Te mp., C,. Pressure, ruins. Hg

Residual Oil:

Per Cent P. Per Cent S Cloud Point, F3

/ 1 Based upon combined weight of reactants.

! Benzene, 200 00s., used as a dil uent. Oils filtered through super-flltrol (clay) to improve color before cloud point determination.

From the results set forth in Table I, above, it 7 will be noted; that when decene-l is reacted with Pass, in the absence of a conjugated hydrocarbon, the yield of oil product is low (run Numbers 1 and 2). Further, run No. 2 also "indicates that with a relatively large amount of phosphorus sulfide reactant, the viscosity index of the oil product decreases and the acidity of the oil product increases markedly. Run No. 3 shows an oil product obtained by reaction of a conjugated hydrocarbon, namely, styrene with P285 in the absence of a normal, alpha mono-olefin; in this instance,

a dark resin is obtained, rather than a viscous oil. Run No. 4 shows the condensation of decenc- 1 with styrene in the absence of a phosphorus sulfide. While the oil product of run No. 4 has an excellent V. I. and pour point, it has an undesirably high cloud point F.)

Run Numbers 5 to 13 illustrate the present invention. Run Numbers 5 and 6 demonstrate the effect of temperature upon the character of the oil products. For example, greater yields are obtained at 600 F. than at 500 F.; the viscosity indices of the oil products are higher when the condensation is carried out at 600 F., as opposed to a reaction temperature of 500 F. Less sulfur and phosphorus are found in the oil products obtained at 600 F. as compared with those formed at 500 F. In each run, the cloud points and P235 is shown by infra-red analyses of the residual oil of run No. 8. Such analyses clearly indicated the presence of aromatic rings in the residual oil.

Runs No. 7, 10 and 11 are comparable and also demonstrate the influence of increased amounts of P235 upon the reaction products. As the amount of P285 is increased, viscosity indices of the synthetic lubricants decreases and acidity thereof increases.

Runs No. 12 and 13 show synthetic lubricants obtained from butadiene, rather than styrene.

The effect of the structure of the mono-olefin reactant is demonstrated by runs No. 14, 15 and 16. Octene-l, octene-2 and 2-ethylhexene-l, respectively, are shown in runs No. 14, 15 and 16. It is clear that the yield is higher when octene- 1 and a normal, alpha mono-olefin is used. Further, the viscosity index of the oil obtained from octene-l is materially higher than that characterizing the oils from octene-2 and 2-eth- 1o product or run No. 4 is materially greater than the viscosity increase of the latter oils.

.To further demonstrate the stability characteristics of the oils of this invention, 3% of the 'ylhexene-l. The oils from the latter two olefins oil product of run was incorporated in a are onl 35 and below 0, respectively. Pennsylvania type lubricating oil and subjected The use of elemental'phosphorus and elemento the catalytic oxidation test described above. tal sulfur, in combination. in place of a Dhos- In this test the blended oil was compared with phorus sulfide, is illus r ed y runs N0. 1' nd the'Pennsylvania lubricating oil alone. The re- 18. When a relatively large amount of phos- 10 sultsof these tests are reported in Table III bephorus and sulfur is used, as in run 18, a lower low."

Table III N. N. N. N. 'Y- Pace PB 8ittiifiifi3f9: 8:? 13' it; 3? at 23 2" it: $223325? Swat: ti?- yield of oil product is realized; in addition, the The results shown in Table III above, reveal V. I.'of the oil is lower. that the synthetic oil of run 10 imparts stability .The synthetic oils contemplated herein, and to the Pennsylvania type lubricating oil. For illustrated above by runs No. 514, 17 and 18, have 25 example, the viscosity increase of the oil blend molecular weights of the order of 1000 or less. is extremely slight, compared with the con- The stability oi. the oils of this invention is rev siderable and undesirable viscosity increase of vealed by the results of a catalytic oxidation the oil blank; Moreover, the lead loss obtained test, to which were subjected several of the rewith the oil blank is appreciably reduced by the sidual oils shown in Table I, above. In this test stabilizing influence of the synthetic oil. 6.5 feet of No. 14 (Brown and Sharpe gauge) As will be evident from the data presented iron wire (15.6 square inch), 62 inches of No. above in Tables I, II and III, the condensation 18 (B. 8t S.) copper wire (0.78 square inch), 3.33 products of this invention are highly desirable inches of No. 12 (B. & S.) aluminum wire (0.87 lubricants per se. They are also of considersquare inch), a 5; inch square of inch lead able value as blending agents for other lubricatsheet (1 5' square inch), and'25 ccs. of the test ing oils. In view of the inherent stability of oil 'were placed in a glass test tube, heated to the synthetic oils, they impart stability to the 260 F. and air blown therethrough at the rate oils with which they are blended. So also, they of 10 liters per hour for 40 hours. impart desirable viscosity index (V. I.) and pour Changes in the characteristics of the oil, sludge 40 point characteristics to the oils in combination formed, and eifects of oil on the copper coil and therewith, for, as indicated above, they have on the lead sheet were reported. On the basis of advantageous viscosity index and pour point these changes, the residual oils were rated as properties. In short, the synthetic oils find compared with a SAE-lO solvent refined Pennutility in upgrading other lubricants. Typisylvania motor oil subjected to the same test. cal oils with Which the Synthet c s y be The results of these tests and of the comparisons blended are mineral oils such as are normally with SAE-lO Pennsylvania motor oil are reported used in internal combustion and turbine engines. inTableIIbelow. When so blended, the synthetic oils may com- Table II Run fgfg; 3 4 a 14 18 Time, Hours-- 40 40 Analyses of Oil:

N. N 16 8, R x. V.@2l0F 12.91 9.44 Percent Viscosity Increa 96. 2-. 0 5 i l ll fio er Co 1' reiiiossi Ira-s11: 3:: 235 238. Rating:

N. N Poor. Fair Viscosity Increase. n Poor Sludge Good Goo Pb. Loss Very Poor--- Very Poor- 1 Indicates oil is very bad in this factor and would probably fail in an engine test.

From inspection of the results shown above in Table II, it will be seen that the new synthetic oils are better than SAE-lO Pennsylvania motor oil in almost all respects. It will be further noted that the residual oil of run No. 4 is obtained by condensation of decene-l with styrene, in the absence of a phosphorus sulfide, and that the oil product therefrom is inferior to the oil products of runs No. 8, 14 and 18, which are oils contemprise the major proportion of the final blended oil, or may even comprise a minor proportion thereof. For example, although used only in the amounts of the order of one to ten per cent,

7 the synthetic oils improve the stability of mineral oils, such as SAE-lO and 20 Pennsylvania type oils.

One or more of the individual properties of the synthetic lubricants of this invention may plated herein. The viscosity increase of the oil 7 be further improved by incorporating therewith a smallybut effective amount, of an addition agent such as an-antioxidant,.a detergent, an extreme pressure agent, a foam suppressor, a viscosity index V. I.) improver, etc..- Antioxidants which may be used are well-known in the art, and are generally characterized by phosphorus, sulfur, nitrogen, etc. content; representative of such materials is a phosphorusand sulfur-containing reaction product of pinene and P285. Typical detergents which may be so used are metal salts of alkyl-substituted aro-, matic sulfonic or carboxylic acids, as illustrated b diwax benzene barium sulfonate and barium phenate, barium carboiwlate of a wax-substituted phenol carboxylic acid. Extreme pressure agents are well known; illustrating such materials are numerous chlorine and/or sulfur containing compositions, one such material, bein a chlor-naphtha xanthate. Silicones, such as dimethyl silicone, may be used to illustrate foam suppressing compositions. Viscosity index improving agents which may be used are typified by polypropylenes, polyisobutylenes, polyacrylate esters, and the like. a

contemplated also as within the scope of this invention is a method of lubricating relatively moving surfaces by maintaining therebetween a film consisting of any of the aforesaid oils.

It is to be understood that the foregoing description and representative examples are nonlimiting and serve to illustrate the invention, which is to be broadly construed in the light of the language of the appended claims.

We claim:

1. The method of preparation of a viscous oil. A

which comprises: condensing, at a temperature between about 500 F. and about 750 F; for a period of time sufficient to efiect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteerf carbon atoms, from about 0.01 to about 1.0 molar proportion of aconjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one -o=o-o=o- I l I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

2. The method of preparation of a viscous oil, which comprises: condensing, at a temperature between about 600 F. and about 700 F. for a period of time sufiicient to eifect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar pro? portion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon bein characterized by at least one grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a sub- 12 stituent is one which is substantially inert in said condensation.

3. The method of preparation of a'viscous oil, which comprises: condensing at a temperature between about 500 F. and about 750 F. for a period of time sufllcient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from eight to twelve carbon atoms, from about 0.01 to about 1.0 molar .proportion bf a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, ofa material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one -o=c-c=o- I I I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

4. The method of preparation of a viscous oil, which comprises: condensing, at a temperature between about 500 F. and about 750 F. for a period of time sufllcient'to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent; by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide,

elemental phosphorus with elemental, sulfur,

the eleatoms; from about 0.01 to about 1.0 molar proportion of a vinyl-substituted aromatic hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof. A

6. The method of preparation of a viscous oil,

- which comprises: condensing, at a temperature between about 500 F. and about 750 F. for a period of time sufllcient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar propor tion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of phosphorus pentasulfide; said conjugated hydrocarbon being characterized by at least one 7. A new composition of matter comprising a condensation product obtained by: condensing, at a temperature between about 500 F. and about 750 F. for a period of time sufficient to eifect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one -c=c o=o I I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

8. A new composition of matter comprising a condensation product obtained by: condensing, at a temperature between about 600 FJand about 700 F. for a period of time sufiicient to effect condensation, one molar proportion of a straight chain, .alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one c=c-c=c- I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

9. A new composition of matter comprising a condensation product obtained by: condensing at a temperature between about 500 .F. and about 750 F. for a period of time sufiicient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from eight to twelve carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one -c=c-o=c- I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

10. A new composition of matter comprising a condensation. product obtained by: condensing, at a temperature between about 500 F. and about 750 F. for a period of time suflicient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total oleflns, of a material selected from'the grou consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof; said conjugated hydrocarbon being characterized by at least one o=c-o=c- I I I I grouping and consisting essentially of the elements carbon and hydrogen.

11. A new composition of matter comprising a condensation product obtained by: condensing, at a temperature between about 500 F. and about 750 F. for a period of time sufiicient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about.

1.0 molar proportion of a vinyl-substituted aromatic hydrocarbon and from about 0.01 to about 10 per cent, by weight of total olefins, of a material selected from the group consisting of a phosphorus sulfide, elemental phosphorus with elemental sulfur, and mixtures thereof.

12. A new composition of matter comprising, a condensation product obtained by: condensing, at a temperature between about 500 F. and about 750 F. for a period of time suflicient to effect condensation, one molar proportion of a straight chain, alpha mono-olefin having from six to fourteen carbon atoms, from about 0.01 to about 1.0 molar proportion of a conjugated hydrocarbon and from about 0.01 to about 10 per cent, by weight of total oleflns, of phosphorus pentasulfide; said conjugated hydrocarbon being characterized by at least one c=c o=c- I I I I grouping and being selected from the group consisting of conjugated hydrocarbons and substituted conjugated hydrocarbons wherein a substituent is one which is substantially inert in said condensation.

13. A viscous oil, obtained by: condensing at about 600 F. for about nine hours, one molar proportion of decene-l with about 0.12 molar proportion of styrene and about 0.0005 molar proportion of phosphorus pentasulfide.

14. A viscous oil, obtained by: condensing at about 600 F. for about nine hours, One molar proportion of decene'-1 with about 0.12 molar proportion of styrene and about 0.002 molar proportion of phosphorus pentasulfide.

15. A viscous oil, obtained by: condensing at about 625 F. for about ten hours, one molar proportion of decene-l with about 0.12 molar proportion of styrene, about 0.006 molar proportion of phosphorus and about 0.02 molar proportion of sulfur.

' WILLIAM E. GARWOOD.

FRANCIS M. SEGER. ALEXANDER N. SACI-IANEN.

/ REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,375,315 Mixon May 8, 1945 2,417,415 Hughes Mar. 18, 194'! 2,424,402 Loane July 22, 1947 2,450,405 Berger Oct. 5, 1948. 

1. THE METHOD OF PREPARATION OF A VISCOUS OIL, WHICH COMPRISES: CONDENSING, AT A TEMPERATURE BETWEEN ABOUT 500*F. AND ABOUT 750*F. FOR A PERIOD OF TIME SUFFICIENT TO EFFECT CONDENSATION, ONE MOLAR PROPORTION OF A STRAIGHT CHAIN, ALPHA MONO-OLEFIN HAVING FROM SIX TO FOURTEEN CARBON ATOMS, FROM ABOUT 0.1 TO ABOUT 1.0 MOLAR PROPORTION OF A CONJUGATED HYDROCARBON AND FROM ABOUT 0.01 TO ABOUT 10 PER CENT, BY WEIGHT OF TOTAL OLEFINS, OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF A PHOSPHORUS SULFIDE, ELEMENTAL PHOSPHORUS WITH ELEMENTAL SULFUR, AND MIXTURES THEREOF; SAID CONJUGATED HYDROCARBON BEING CHARACTERIZED BY AT LEAST ONE 